We have observed photoexcitation of the dipole-forbidden 1s(2) 1S0-->2p(2) 1D2 resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2l2l(') autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p 1P1 and 2p(2) 1D2 levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q(2) to be markedly different from theoretical expectations.
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http://dx.doi.org/10.1103/PhysRevLett.88.203002 | DOI Listing |
Sci Adv
May 2022
Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie, Max-Born-Straße 2A, 12489 Berlin, Germany.
Extending nonlinear spectroscopic techniques into the x-ray domain promises unique insight into photoexcited charge dynamics, which are of fundamental and applied interest. We report on the observation of a third-order nonlinear process in lithium fluoride (LiF) at a free-electron laser. Exploring the yield of four-wave mixing (FWM) in resonance with transitions to strongly localized core exciton states versus delocalized Bloch states, we find resonant FWM to be a sensitive probe for the degree of charge localization: Substantial sum- and difference-frequency generation is observed exclusively when in a one- or three-photon resonance with a LiF core exciton, with a dipole forbidden transition affecting details of the nonlinear response.
View Article and Find Full Text PDFFaraday Discuss
September 2013
Department of Chemistry, University of Warwick, Library Road, Coventry CV4 7AL, UK.
The heteroaromatic ultraviolet chromophore pyrrole is found as a subunit in a number of important biomolecules: it is present in heme, the non-protein component of hemoglobin, and in the amino acid tryptophan. To date there have been several experimental studies, in both the time- and frequency-domains, which have interrogated the excited state dynamics of pyrrole. In this work, we specifically aim to unravel any differences in the H-atom elimination dynamics from pyrrole across an excitation wavelength range of 250-200 nm, which encompasses: (i) direct excitation to the (formally electric dipole forbidden) 1(1)pisigma* (1A2) state; and (ii) initial photoexcitation to the higher energy 1 pipi* (1B2) state.
View Article and Find Full Text PDFPhys Rev Lett
March 2013
Department of Electrical and Computer Engineering, Rice University, Houston, Texas 77005, USA.
We use terahertz pulses to induce resonant transitions between the eigenstates of optically generated exciton populations in a high-quality semiconductor quantum well sample. Monitoring the excitonic photoluminescence, we observe transient quenching of the 1s exciton emission, which we attribute to the terahertz-induced 1s-to-2p excitation. Simultaneously, a pronounced enhancement of the 2s exciton emission is observed, despite the 1s-to-2s transition being dipole forbidden.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2012
Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, Tokyo 102-8554, Japan. sh
On-the-fly nonadiabatic ab initio molecular dynamics simulations have been carried out for three anionic species of indolylmaleimides (3-(1H-3-indolyl)-2,5-dihydro-1H-2,5-pyrroledione, IM) to clarify the mechanisms of photochemical reactions. The results are obtained for (i) a monovalent anion with a deprotonated indole NH group (IM(-)'), (ii) a monovalent anion with a deprotonated maleimide NH group (IM(-)'') and (iii) a divalent anion with doubly deprotonated indole and the maleimide NH groups (IM(2-)). Quantum chemical calculations are treated at the three state averaged complete-active space self-consistent field level for 6 electrons in 5 orbitals with the cc-pVDZ basis set (CAS (6, 5) SCF/cc-pVDZ).
View Article and Find Full Text PDFPhys Rev Lett
May 2002
Argonne National Laboratory, Argonne, Illinois 60439, USA.
We have observed photoexcitation of the dipole-forbidden 1s(2) 1S0-->2p(2) 1D2 resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2l2l(') autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p 1P1 and 2p(2) 1D2 levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q(2) to be markedly different from theoretical expectations.
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